CN102911196A - Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester - Google Patents
Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester Download PDFInfo
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- CN102911196A CN102911196A CN2012104671612A CN201210467161A CN102911196A CN 102911196 A CN102911196 A CN 102911196A CN 2012104671612 A CN2012104671612 A CN 2012104671612A CN 201210467161 A CN201210467161 A CN 201210467161A CN 102911196 A CN102911196 A CN 102911196A
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- preparation
- trifluoromethanesulfonic acid
- trimethylchlorosilane
- dimethylchlorosilane
- trimethylsilyl ester
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Abstract
The invention relates to a preparation method of trifluoromethanesulfonic acid trimethylsilyl ester. The preparation method comprises the following steps of: adding trifluoromethanesulfonate into a silylation reagent according to the molar ratio of 1:(1.5-4), keeping the reaction temperature at -15 DEG C-40 DEG C, adding a calcium chloride drying pipe on a reflux condensing pipe, performing stirring reaction for 1-10h, and finally rectifying and collecting products obtained at the temperature of 135 DEG C-145 DEG C. The preparation method of the trifluoromethanesulfonic acid trimethylsilyl ester, disclosed by the invention, has the characteristics of simplicity, quickness and easiness in operation; although trimethylchlorosilane also contains dimethylchlorosilane impurities, the trimethylchlorosilane can inhibit the dimethylchlorosilane and other impurities from reacting with trifluoromethanesulfonic acid; and furthermore, the trimethylchlorosilane can react with the trifluoromethanesulfonate, the dimethylchlorosilane can be recovered very easily after rectification, and the trifluoromethanesulfonic acid trimethylsilyl ester with the purity of above 99.9% can be simultaneously prepared.
Description
Technical field
The present invention relates to a kind of preparation method of trimethylsilyl triflate.
Background technology
Trimethylsilyl triflate is that the people such as Schmeisser is synthetic first in 1970, owing to its reactive behavior becomes by force a kind of silylation reagent that is widely used in organic synthesis.In organic synthesis, mainly contain the effect of the following aspects: 1, in organic synthesis for the protection of functional group, be highly effective methyl-monosilane base reagent; 2, in organic synthesis, participate in multiple organic compound carbon carbon and become key to increase the reaction of carbochain; 3, in some reaction, make catalyzer.Trimethylsilyl triflate mainly was by trifluoromethanesulfonic acid and tetramethylsilane reaction preparation in the past, but tetramethylsilane often can be brought the impurity such as a large amount of dimethylbutanes, dimethylchlorosilane, dimethyl dichlorosilane (DMCS) in process of production, these impurity and the trifluoromethanesulfonic acid generation by product that reacts.Particularly the boiling point of the trifluoromethanesulfonic acid dimethyl estersil of dimethylchlorosilane and trifluoromethanesulfonic acid generation and trimethylsilyl triflate is very approaching, be difficult to separate with the method for rectifying, bring many difficulties can for preparation and the purifying of trimethylsilyl triflate.
Summary of the invention
Purpose of the present invention just provides the preparation method of a kind of simple and fast, easy handling, trimethylsilyl triflate that the preparation product purity is high.
The preparation method of trimethylsilyl triflate of the present invention, be with fluoroform sulphonate in molar ratio 1:1.5-4 join in the silylation reagent, temperature of reaction is-15 ℃-40 ℃, add calcium chloride tube on the reflux condensing tube, stirring reaction 1-10h, by rectifying, collect 135 ℃ of-145 ℃ of products that obtain at last.
Described fluoroform sulphonate structural formula is: CF
3SO
3M, wherein M is Li, Na, K, the best is trifluoromethanesulfonic acid potassium.
Described silylation reagent is TMSX, and TMS refers to that trimethyl silane, X are Cl, Br or I.
Reaction scheme is as follows:
CF
3SO
3M + TMSX → CF
3SO
3TMS X = Cl, Br, I。
The preparation method of trimethylsilyl triflate of the present invention, characteristics with simple and fast, easy handling, although trimethylchlorosilane also contains dimethylchlorosilane impurity, but trimethylchloro-silicane can suppress the reaction of the impurity such as dimethylchlorosilane and trifluoromethanesulfonic acid to be occured, and trimethylchlorosilane and trifluoromethanesulfonic acid reactant salt, can be recovered to easily dimethylchlorosilane through after the rectifying, prepare simultaneously purity at the trimethylsilyl triflate more than 99.9%.
Embodiment
Embodiment 1
The trifluoromethanesulfonic acid potassium of 2mol is joined in the trimethylchlorosilane of 2.06 mol, at 25 ℃ of lower stirring reaction 1h, add calcium chloride tube on the reflux condensing tube, react cut 14.1449 g that 135 ℃-145 ℃ of top temperature are collected in complete rear underpressure distillation, productive rate reaches 90%, purity 99.95%.
Embodiment 2
With trifluoromethanesulfonic acid lithium solid state powder 312g, join in the 3mol Iodotrimethylsilane, 30 ℃ of lower stirring reaction 6h add calcium chloride tube on the reflux condensing tube.React complete rear underpressure distillation and collect the cut 695.2g of 135 ℃-145 ℃ of top temperature, productive rate reaches 90.5%, purity 99.92%.
Embodiment 3
Join in the 50L vial with the bromotrimethylsilane of the trifluoromethanesulfonic acid sodium of 150 mol and 175 mol and to react, at-10 ℃ of lower stirring reaction 5h, connecing offgas duct on the reflux exchanger is passed in the calcium chloride drying bottle, reaction changes in the rectifier unit after finishing, control reflux ratio 2:1,130-145 ℃ cut 29.8kg is collected in underpressure distillation, productive rate 89.4%, and purity reaches 99.9%.
Claims (3)
1. the preparation method of a trimethylsilyl triflate, it is characterized in that: it be with fluoroform sulphonate in molar ratio 1:1.5-4 join in the silylation reagent, temperature of reaction is-15 ℃-40 ℃, add calcium chloride tube on the reflux condensing tube, stirring reaction 1-10h, by rectifying, collect 135 ℃ of-145 ℃ of products that obtain at last;
Described fluoroform sulphonate structural formula is: CF
3SO
3M, wherein M is Li, Na, K;
Described silylation reagent is TMSX, and TMS refers to that trimethyl silane, X are Cl, Br or I.
2. the preparation method of trimethylsilyl triflate according to claim 1, it is characterized in that: described fluoroform sulphonate is trifluoromethanesulfonic acid potassium.
3. the preparation method of trimethylsilyl triflate according to claim 1, it is characterized in that: described silylation reagent is trimethylchlorosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2012104671612A CN102911196A (en) | 2012-11-19 | 2012-11-19 | Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester |
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| CN2012104671612A CN102911196A (en) | 2012-11-19 | 2012-11-19 | Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester |
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| CN102911196A true CN102911196A (en) | 2013-02-06 |
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| CN2012104671612A Pending CN102911196A (en) | 2012-11-19 | 2012-11-19 | Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588803A (en) * | 2013-10-14 | 2014-02-19 | 青岛文创科技有限公司 | Preparation method of trimethylsilyl trifluoromethanesulfonate |
| CN103665017A (en) * | 2013-12-12 | 2014-03-26 | 中国船舶重工集团公司第七一八研究所 | Preparation method of Trimethylsilyl trifluoromethanesulfonate |
| CN104262376A (en) * | 2014-10-16 | 2015-01-07 | 中国船舶重工集团公司第七一八研究所 | TMSOTf (trimethylsilyl trifluoromethanesulfonate) purifying method |
| CN108373481A (en) * | 2017-11-30 | 2018-08-07 | 江西国化实业有限公司 | A kind of preparation method of Trimethylsilyl trifluoromethanesulfonate |
| EP3412659A1 (en) | 2017-06-09 | 2018-12-12 | Solvay Sa | Processes for the manufacture of sulfur-substituted pyrazole derivatives |
| CN114394989A (en) * | 2022-03-08 | 2022-04-26 | 中船(邯郸)派瑞特种气体股份有限公司 | Preparation method of triisopropyl silicon-based trifluoromethanesulfonate |
Citations (3)
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|---|---|---|---|---|
| CN1291985A (en) * | 1998-02-27 | 2001-04-18 | 罗狄亚化学公司 | Method for triflic acid silylation |
| WO2006012425A2 (en) * | 2004-07-21 | 2006-02-02 | Corixa Corporation | Processes for the production of aminoalkyl glucosaminide phosphate and disaccharide immunoeffectors, and intermediates therefor |
| CN1847250A (en) * | 2005-04-15 | 2006-10-18 | 大连思谱精工有限公司 | Silane reagent with high reaction activity and its prepn process |
-
2012
- 2012-11-19 CN CN2012104671612A patent/CN102911196A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1291985A (en) * | 1998-02-27 | 2001-04-18 | 罗狄亚化学公司 | Method for triflic acid silylation |
| WO2006012425A2 (en) * | 2004-07-21 | 2006-02-02 | Corixa Corporation | Processes for the production of aminoalkyl glucosaminide phosphate and disaccharide immunoeffectors, and intermediates therefor |
| CN1847250A (en) * | 2005-04-15 | 2006-10-18 | 大连思谱精工有限公司 | Silane reagent with high reaction activity and its prepn process |
Non-Patent Citations (2)
| Title |
|---|
| R. D. HOWELLS等: "Trifluorornethanesulfonic Acid and Derivatives", 《CHEMICAL REVIEWS》, vol. 77, no. 1, 1 February 1977 (1977-02-01), pages 77 - 2 * |
| 李增春: "三氟甲磺酸三甲硅脂的回收重制", 《化学试剂》, vol. 20, no. 1, 28 February 1998 (1998-02-28), pages 60 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588803A (en) * | 2013-10-14 | 2014-02-19 | 青岛文创科技有限公司 | Preparation method of trimethylsilyl trifluoromethanesulfonate |
| CN103665017A (en) * | 2013-12-12 | 2014-03-26 | 中国船舶重工集团公司第七一八研究所 | Preparation method of Trimethylsilyl trifluoromethanesulfonate |
| CN103665017B (en) * | 2013-12-12 | 2016-08-17 | 中国船舶重工集团公司第七一八研究所 | A kind of preparation method of Trimethylsilyl trifluoromethanesulfonate |
| CN104262376A (en) * | 2014-10-16 | 2015-01-07 | 中国船舶重工集团公司第七一八研究所 | TMSOTf (trimethylsilyl trifluoromethanesulfonate) purifying method |
| EP3412659A1 (en) | 2017-06-09 | 2018-12-12 | Solvay Sa | Processes for the manufacture of sulfur-substituted pyrazole derivatives |
| CN108373481A (en) * | 2017-11-30 | 2018-08-07 | 江西国化实业有限公司 | A kind of preparation method of Trimethylsilyl trifluoromethanesulfonate |
| CN114394989A (en) * | 2022-03-08 | 2022-04-26 | 中船(邯郸)派瑞特种气体股份有限公司 | Preparation method of triisopropyl silicon-based trifluoromethanesulfonate |
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Application publication date: 20130206 |